CN108504354A - A kind of preparation method of silicon doped graphene quantum dot - Google Patents
A kind of preparation method of silicon doped graphene quantum dot Download PDFInfo
- Publication number
- CN108504354A CN108504354A CN201810231349.4A CN201810231349A CN108504354A CN 108504354 A CN108504354 A CN 108504354A CN 201810231349 A CN201810231349 A CN 201810231349A CN 108504354 A CN108504354 A CN 108504354A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- silicon doped
- added
- distilled water
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of silicon doped graphene quantum dot.（1）By H2SO4With the P of 1g2O5It stirs and evenly mixs, is heated to 80 DEG C and is slowly added into 2g graphite powders, 80 DEG C are continued to heat 6 hours postcoolings to room temperature；Then it is diluted with distilled water, filters and cleaning is up to neutral repeatedly, drying under nitrogen protection.（2）By the KMnO of 6g4Powder is added to H2SO4In, add step（1）Products therefrom；Stirring；Distilled water is added, adds distilled water after stirring again；Add H2O2, filter, be washed till neutral dry to get graphene oxide.（3）By silicon source and step（2）Gained graphene oxide in water ultrasound uniformly after, carry out hydro-thermal reaction；Filtering, dialysis, freeze-drying obtain silicon doped graphene quantum dot.Present invention process is simple, easy to operate, and the silicon doped graphene quantum dot morphology controllable of preparation, particle size dispersion is uniform, has stable fluorescence property.
Description
Technical field
The present invention relates to a kind of preparation methods of the silicon doped graphene quantum dot with green light performance.
Background technology
Graphene quantum dot（Graphene Quantum Dot, GQDs）, since its significant fluorescent characteristic is by extensive
Concern, it is theoretical and it is demonstrated experimentally that GQDs is also equipped with stronger quantum confinement other than having the unique property of graphene itself
Effect and edge effect have preferable application prospect in photoelectric device, sensor, bio-imaging etc..It is disadvantageous that
The active site of the GQDs synthesized at present is relatively fewer, fluorescence quantum yield is low, selectivity is not high, limits to a certain extent
Popularization, the application of GQDs.Studies have shown that exotic atom enters graphene-structured, band gap not only can be effectively introduced, but also can increase
The defect of graphene and the reactivity of local, to induce many special physicochemical properties.Currently, the preparation of doping type GQDs
And its research of mechanism is scarcely out of swaddling-clothes, therefore, probe into doping type GQDs preparation and doping to the structure of GQDs and
The regulation and control of performance have great significance of scientific research and application value.
Invention content
It is an object of the present invention to provide a kind of preparation methods of silicon doped graphene quanta point material, by sodium metasilicate and oxidation stone
Fluorescence property can be improved by hydro-thermal reaction in black alkene solution.Present invention process is simple, easy to operate, the silicon doped graphite of preparation
Alkene quantum dot morphology controllable, particle size dispersion are uniform.
The specific steps are：
（1）The H for being 98% by 10 mL mass percent concentrations2SO4With the P of 1g2O5It is placed in round-bottomed flask, stirs and evenly mixs, add
Heat is slowly added into 2g graphite powders to 80 DEG C, and 80 DEG C are continued to heat 6 hours postcoolings to room temperature；Then it is diluted, is filtered with distilled water
And cleaning is dry under nitrogen protection up to neutral repeatedly.
（2）Under condition of ice bath, by the KMnO of 6g4It is 98% that powder, which is slowly added into 46 mL mass percent concentrations,
H2SO4In, step is slow added into after mixing（1）Products therefrom；Whole process ensures that bath temperature is maintained at 0 ~ 20 DEG C, mixes
After even, continue stirring 4 hours in 35 DEG C of water-baths, forms brown paste；100 mL distilled water are added, after stirring 30 minutes again
Add 300mL distilled water；Finally 12 mL are added to analyze pure H dropwise2O2, solution is in glassy yellow, is filtered while hot, distillation water wash precipitation
Object is dried until being put into after neutral in vacuum drying chamber to get graphene oxide（GO）Solid.
（3）By step（2）Gained graphene oxide（GO）Solid adds water to be configured to the oxidation of a concentration of 0.1 ~ 2.0 mg/mL
Graphene solution.
（4）By 0.01 ~ 1.5g silicon sources and 10mL steps（3）The graphene oxide of a concentration of 0.1 ~ 2.0 mg/mL of gained exists
After ultrasound is uniform in water, mixed liquor is transferred in the polytetrafluoroethylene (PTFE) stainless steel steel reaction kettle that volume is 20 ~ 200mL in temperature
Hydro-thermal reaction is carried out for 120 ~ 200 DEG C 4 ~ 8 hours；After reaction, it filters, dialyse, freeze-drying obtains silicon doped graphite
Alkene quantum dot.
The silicon source is one kind in silicic acid, sodium metasilicate, silica and ethyl orthosilicate.
Compared with prior art, the beneficial effects of the present invention are：
The graphite powder that the present invention selects price cheap is as raw material, using the nontoxic oxidation of simple hydro-thermal method synthesizing environment-friendly first
Then graphene prepares silicon doped graphene quantum dot with silicon source by hydro-thermal reaction, wherein the zero-dimension nano by silicon modification
Structure graphite alkene quantum dot is not only significantly improved with strong fluorescence performance, and Relative quantum yields reach 8.62%, and grain size exists
It 15nm or so and is uniformly dispersed.Silicon doped graphene quanta point material prepared by this method has in bio-sensing and bio-imaging
Wide application prospect.The safety of this preparation method is good, of low cost, environmentally friendly, excellent optical performance, is suitable for industry
Metaplasia is produced.
Description of the drawings
Fig. 1 is the TEM design sketch for the silicon doped graphene quantum dot that the embodiment of the present invention obtains.
Fig. 2 is picture of the obtained silicon doped graphene quantum dot of the embodiment of the present invention under ultra violet lamp.
Fig. 3 is picture of the obtained silicon doped graphene quantum dot of the embodiment of the present invention under natural light irradiation.
Fig. 4 is the infrared spectrogram for the silicon doped graphene quantum dot that the embodiment of the present invention obtains.
Fig. 5 is the abosrption spectrogram for the silicon doped graphene quantum dot that the embodiment of the present invention obtains.
Fig. 6 is the fluorescence emission spectrogram of compound for the silicon doped graphene quantum dot that the embodiment of the present invention obtains.
Specific implementation mode
Embodiment：
（1）The H for being 98% by 10 mL mass percent concentrations2SO4With the P of 1g2O5It is placed in round-bottomed flask, stirs and evenly mixs, add
Heat is slowly added into 2g graphite powders to 80 DEG C, and 80 DEG C are continued to heat 6 hours postcoolings to room temperature；Then it is diluted, is filtered with distilled water
And cleaning is dry under nitrogen protection up to neutral repeatedly.
（2）Under condition of ice bath, by the KMnO of 6g4It is 98% that powder, which is slowly added into 46 mL mass percent concentrations,
H2SO4In, step is slow added into after mixing（1）Products therefrom；Whole process ensures that bath temperature is maintained at 15 DEG C, after mixing,
Continue stirring 4 hours in 35 DEG C of water-baths, forms brown paste；100 mL distilled water are added, stirring adds again after 30 minutes
300mL distilled water；Finally 12 mL are added to analyze pure H dropwise2O2, solution is in glassy yellow, is filtered while hot, and water wash sediment is distilled
It is dried to get graphene oxide until being put into after neutral in vacuum drying chamber（GO）Solid.
（3）By step（2）Gained graphene oxide（GO）Solid adds water to be configured to the graphite oxide of a concentration of 1.5mg/mL
Alkene solution.
（4）By 0.1g sodium metasilicate and 10mL steps（3）The graphene oxide of a concentration of 1.5mg/mL of gained is ultrasonic in water
After uniformly, it is 180 DEG C of progress that mixed liquor, which is transferred in the polytetrafluoroethylene (PTFE) stainless steel steel reaction kettle that volume is 200mL in temperature,
Hydro-thermal reaction 5 hours；After reaction, it filters, dialyse, freeze-drying obtains silicon doped graphene quantum dot.
The Si-GQDs of synthesis is can be seen that in more single point uniform from the TEM images of the Si-GQDs of Fig. 1
Bulk state, Average Particle Diameters are about 15nm.
From Fig. 2 it is observed that green fluorescence can be observed under 365 nm ultraviolet lamps.
From Fig. 3 it is observed that light brown quantum dot aqueous solution can be observed under natural light.
Shown in infrared spectrogram from Fig. 4, Si-GQDs is in 3447cm-1The peak at place shakes corresponding to the flexible of O-H and N-H
It is dynamic, show that there are carboxyl and amino, 2928cm on the surfaces Si-GQDs synthesized-1Peak be then C-H stretching vibration peak,
1637cm-1And 1383cm-1Absorption peak, the symmetric vibration of the stretching vibration and carboxylic acid of C=O, 1044cm can be classified as respectively-1With
878cm-1Can be attributed to the symmetrical stretching vibration absorption peak of Si-O-Si key antisymmetric stretching vibration Si-O-Si keys, it is provable
During synthesizing Si-GQDs, the sp of part in graphene oxide2The carbon of hydridization is transformed to sp3Hydridization carbon.And silicon member
Element is successfully doped in GQDs.
From Figures 5 and 6 it can be seen that：The aqueous solution of Si-GQDs has stronger absorption in ultra-violet (UV) band, but without apparent feature
It absorbs；The maximum excitation and emission peak of Si-GQDs is located at 310 nm and 440 nm.Si-GQDs stoste fluorescence intensities reach
To 21600.
Claims (1)
1. a kind of preparation method of silicon doped graphene quantum dot, it is characterised in that the specific steps are：
（1）The H for being 98% by 10 mL mass percent concentrations2SO4With the P of 1g2O5It is placed in round-bottomed flask, stirs and evenly mixs, add
Heat is slowly added into 2g graphite powders to 80 DEG C, and 80 DEG C are continued to heat 6 hours postcoolings to room temperature；Graphite powder is diluted with distilled water, mistake
It filters and cleaning is up to neutral repeatedly, drying under nitrogen protection；
（2）Under condition of ice bath, by the KMnO of 6g4Powder is slowly added into the H that 46 mL mass percent concentrations are 98%2SO4
In, step is slow added into after mixing（1）Gained graphite powder；Whole process ensures that bath temperature is maintained at 0 ~ 20 DEG C, mixing
Afterwards, continue stirring 4 hours in 35 DEG C of water-baths, form brown paste；100 mL distilled water are added, stirring adds again after 30 minutes
300mL distilled water；Finally 12 mL are added to analyze pure H dropwise2O2, solution is in glassy yellow, is filtered while hot, and water wash sediment is distilled
It is dried to get graphene oxide solid until being put into after neutral in vacuum drying chamber；
（3）By step（2）The graphene oxide that gained graphene oxide solid adds water to be configured to a concentration of 0.1 ~ 2.0 mg/mL is molten
Liquid；
（4）By 0.01 ~ 1.5g silicon sources and 10mL steps（3）The graphene oxide of a concentration of 0.1 ~ 2.0 mg/mL of gained is in water
After ultrasound is uniform, mixed liquor is transferred to volume to be in temperature in the polytetrafluoroethylene (PTFE) stainless steel steel reaction kettle of 20 ~ 200mL
120 ~ 200 DEG C carry out hydro-thermal reaction 4 ~ 8 hours；After reaction, it filters, dialyse, freeze-drying obtains silicon doped graphene
Quantum dot；
The silicon source is one kind in silicic acid, sodium metasilicate, silica and ethyl orthosilicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810231349.4A CN108504354A (en) | 2018-03-20 | 2018-03-20 | A kind of preparation method of silicon doped graphene quantum dot |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810231349.4A CN108504354A (en) | 2018-03-20 | 2018-03-20 | A kind of preparation method of silicon doped graphene quantum dot |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108504354A true CN108504354A (en) | 2018-09-07 |
Family
ID=63377088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810231349.4A Pending CN108504354A (en) | 2018-03-20 | 2018-03-20 | A kind of preparation method of silicon doped graphene quantum dot |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108504354A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113277499A (en) * | 2021-05-07 | 2021-08-20 | 优彩科技(湖北)有限公司 | Preparation method and application of silicon-nitrogen co-doped graphene quantum dot |
| WO2022142582A1 (en) * | 2020-12-31 | 2022-07-07 | 广东邦普循环科技有限公司 | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| CN114751400A (en) * | 2022-05-23 | 2022-07-15 | 湖北工业大学 | Nitrogen and zinc co-doped graphene quantum dot, ratio type immunosensor, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351173A (en) * | 2011-07-13 | 2012-02-15 | 武汉大学 | Method for preparing high quality graphene in large scale |
| CN107474821A (en) * | 2016-06-07 | 2017-12-15 | 上海交通大学 | A kind of Silica-coated quantum dot and preparation method thereof |
-
2018
- 2018-03-20 CN CN201810231349.4A patent/CN108504354A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351173A (en) * | 2011-07-13 | 2012-02-15 | 武汉大学 | Method for preparing high quality graphene in large scale |
| CN107474821A (en) * | 2016-06-07 | 2017-12-15 | 上海交通大学 | A kind of Silica-coated quantum dot and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| TING WEN等: "Organosilane-functionalized graphene quantum dots and their encapsulation into bi-layer hollow silica spheres for bioimaging applications", 《PHYS.CHEM.CHEM.PHYS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142582A1 (en) * | 2020-12-31 | 2022-07-07 | 广东邦普循环科技有限公司 | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| GB2616799A (en) * | 2020-12-31 | 2023-09-20 | Guangdong Brunp Recycling Technology Co Ltd | Silicon-doped graphene composite material, preparation method for same, and applications thereof |
| CN113277499A (en) * | 2021-05-07 | 2021-08-20 | 优彩科技(湖北)有限公司 | Preparation method and application of silicon-nitrogen co-doped graphene quantum dot |
| CN113277499B (en) * | 2021-05-07 | 2022-11-08 | 优彩科技(湖北)有限公司 | Preparation method and application of silicon-nitrogen co-doped graphene quantum dots |
| CN114751400A (en) * | 2022-05-23 | 2022-07-15 | 湖北工业大学 | Nitrogen and zinc co-doped graphene quantum dot, ratio type immunosensor, and preparation method and application thereof |
| CN114751400B (en) * | 2022-05-23 | 2023-08-25 | 湖北工业大学 | Nitrogen-zinc co-doped graphene quantum dot, ratio immunosensor and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192604A (en) | A kind of preparation method of nitrogen-doped graphene quantum dot | |
| Velmurugan et al. | Extraction, characterization, and catalytic potential of amorphous silica from corn cobs by sol-gel method | |
| CN108504354A (en) | A kind of preparation method of silicon doped graphene quantum dot | |
| TWI295682B (en) | Surface-modified non-metal/metal oxides coated with silicon dioxide | |
| CN102350334B (en) | Graphene/mesoporous titanium dioxide visible light catalyst and preparation method | |
| CN106517341B (en) | A kind of method and its application for preparing manganese dioxide nano catalyst | |
| CN104071769A (en) | Method for preparing fluorescent carbon point by virtue of chemical oxidation method, fluorescent carbon point and application of fluorescent carbon point | |
| CN106244142B (en) | A kind of preparation method of fluorescent carbon quantum dot polymer hybrid material | |
| Hussin et al. | Photocatalytic synthesis of reduced graphene oxide-zinc oxide: effects of light intensity and exposure time | |
| CN107774294A (en) | A kind of novel photochemical catalyst K g C3N4And its prepare and apply | |
| Maaoui et al. | A Prussian blue/carbon dot nanocomposite as an efficient visible light active photocatalyst for CH activation of amines | |
| CN106829920A (en) | A kind of green fluorescence carbon quantum dot material and preparation method thereof | |
| CN109395763A (en) | A kind of sulfur doping g-C3N4Porous composite photo-catalyst of/C-dot and the preparation method and application thereof | |
| CN109735324A (en) | A kind of method that in-situ method prepares mesoporous silicon dioxide modified carbon dots | |
| CN104530089A (en) | Fluorescent molecular TPCA and preparation method thereof | |
| CN107353896A (en) | A kind of method that carbon point is prepared using apple skin | |
| CN106916589A (en) | A kind of method that fluorescent carbon point is prepared by waste material longan shell | |
| Yang et al. | Synthesis, characterization and photocatalytic activities of a novel Eu/TiO2/GO composite, and its application for enhanced photocatalysis of methylene blue | |
| CN109046421B (en) | It is a kind of to prepare C, N co-doped nano pipe/stick catalysis material method using quaternary ammonium base | |
| CN107089679B (en) | A kind of self-template prepares sheet using alkyd dehydration microwave in-situ and inlays a cube hollow TiO2Nanocrystalline method | |
| CN108358187A (en) | A kind of preparation method of the golden yellow fluorescent carbon point of hair | |
| CN104475159B (en) | Preparation method and application of 1-3-generation poly (aryl ether) dendritic phthalocyanine complex loaded SiO2 visible light photocatalyst | |
| CN105883829A (en) | Method for synthesizing onion mesoporous silica nanometer material | |
| CN109261180A (en) | Utilize the Ti of dimethyl sulfoxide intercalation and layering3C2Fabricated in situ TiO2@Ti3C2Method and product | |
| CN113403068A (en) | Fused carbon dot, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180907 |
|
| RJ01 | Rejection of invention patent application after publication |